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In 1529, Georgius Agricola described fluorite as an additive used to lower the melting point of metals during smelting. He penned the Latin word fluorēs (fluor, flow) for fluorite rocks. The name later evolved into fluorspar (still commonly used) and then fluorite. The composition of fluorite was later determined to be calcium difluoride.
Hydrofluoric acid was used in glass etching from 1720 onward. Andreas Sigismund Marggraf first characterized it in 1764 when he heated fluorite with sulfuric acid, and the resulting solution corroded its glass container. Swedish chemist Carl Wilhelm Scheele repeated the experiment in 1771, and named the acidic product fluss-spats-syran (fluorspar acid). In 1810, the French physicist André-Marie Ampère suggested that hydrogen and an element analogous to chlorine constituted hydrofluoric acid. He also proposed in a letter to Sir Humphry Davy dated August 26, 1812 that this then-unknown substance may be named fluorine from fluoric acid and the -ine suffix of other halogens. This word, often with modifications, is used in most European languages; however, Greek, Russian, and some others, following Ampère's later suggestion, use the name ftor or derivatives, from the Greek φθόριος (phthorios, destructive). The New Latin name fluorum gave the element its current symbol F; Fl was used in early papers.
Isolation
Initial studies on fluorine were so dangerous that several 19th-century experimenters were deemed "fluorine martyrs" after misfortunes with hydrofluoric acid. Isolation of elemental fluorine was hindered by the extreme corrosiveness of both elemental fluorine itself and hydrogen fluoride, as well as the lack of a simple and suitable electrolyte. Edmond Frémy postulated that electrolysis of pure hydrogen fluoride to generate fluorine was feasible and devised a method to produce anhydrous samples from acidified potassium bifluoride; instead, he discovered that the resulting (dry) hydrogen fluoride did not conduct electricity. Frémy's former student Henri Moissan persevered, and after much trial and error found that a mixture of potassium bifluoride and dry hydrogen fluoride was a conductor, enabling electrolysis. To prevent rapid corrosion of the platinum in his electrochemical cells, he cooled the reaction to extremely low temperatures in a special bath and forged cells from a more resistant mixture of platinum and iridium, and used fluorite stoppers. In 1886, after 74 years of effort by many chemists, Moissan isolated elemental fluorine.
In 1906, two months before his death, Moissan received the Nobel Prize in Chemistry, with the following citation:
[I]n recognition of the great services rendered by him in his investigation and isolation of the element fluorine ... The whole world has admired the great experimental skill with which you have studied that savage beast among the elements.
Later uses
The Frigidaire division of General Motors (GM) experimented with chlorofluorocarbon refrigerants in the late 1920s, and Kinetic Chemicals was formed as a joint venture between GM and DuPont in 1930 hoping to market Freon-12 (CCl2F2) as one such refrigerant. It replaced earlier and more toxic compounds, increased demand for kitchen refrigerators, and became profitable; by 1949 DuPont had bought out Kinetic and marketed several other Freon compounds. Polytetrafluoroethylene (Teflon) was serendipitously discovered in 1938 by Roy J. Plunkett while working on refrigerants at Kinetic, and its superlative chemical and thermal resistance lent it to accelerated commercialization and mass production by 1941.
Large-scale production of elemental fluorine began during World War II. Germany used high-temperature electrolysis to make tons of the planned incendiary chlorine trifluoride and the Manhattan Project used huge quantities to produce uranium hexafluoride for uranium enrichment. Since UF
6 is as corrosive as fluorine, gaseous diffusion plants required special materials: nickel for membranes, fluoropolymers for seals, and liquid fluorocarbons as coolants and lubricants. This burgeoning nuclear industry later drove post-war fluorochemical development.
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